Novel resinous compositions and method for producing same

ABSTRACT

This invention relates to certain novel curable resinous compositions of matter comprising (A) an organic polyepoxide having a molecular weight ranging from about 1000-2000 and (B) a primary or secondary amine containing hydroxyl groups and a method for producing the same. These resinous compositions of matter may be cured into useful protective coatings at low ambient temperatures through the use of polyisocyanates as curing agents.

nited States atent [191 Mallavarapu 1 Jan. 22, 11974 [75] Inventor: LeoX. Mallavarapu, Suffern, NY.

[73] Assignee: Reichhold Chemicals, Inc., White Plains, NY.

[22] Filed: Feb. 18, 1972 [21] Appl. No.: 227,656

[52] US. Cl. 260/304 EP, 260/328 EP, 360/338 EP, 260/37 EP [51] Int.Cl... C08g 51/26, C08g 51/34, C08g 51/30 [58] Field of Search 260/47 EN,31.4 EP, 47 CB, 260/336 EP, 32.8 EP

[56] References Cited UNITED STATES PATENTS 3,538,039 11/1970 Lantz eta1. 260/47 EN X 3,454,421 7/1969 Westbrook 260/47 EN X 3,321,548 5/1967Sattler 260/47 EN X 3,367,991 2/1968 Hicks 260/47 EN X PrimaryExaminer-Lewis T. Jacobs Attorney, Agent, or FirmMunson H. Lane et a1.

[5 7] ABSTRACT This invention relates to certain novel curable resinouscompositions of matter comprising (A) an organic polyepoxide having amolecular weight ranging from about 1000-2000 and (B) a primary orsecondary amine containing hydroxyl groups and a method for producingthe same. These resinous compositions of matter may be cured into usefulprotective coatings at low ambient temperatures through the use ofpolyisocyanates as curing agents.

4 Claims, N0 Drawings er .m d ssrs iltttsraasr ss a l?!sh 99. 2.-

NOVEL IRESINOUS cOMPOsrTroNs AND METHOD FOR PRODUCING SAME except atelevated temperatures (160 C) with nbutoxylithium as a catalyst ando'-dichlorobenzene as a This invention discloses certain novel curableresinous compositions of matter and a method for producing the same.These resinous compositions of matter may be cured into tough, chemicalresistant, protective coatings at low ambient temperatures through theuse of polyisocyanates as curing agents. Compositions contemplated byinstant invention comprise reacting (A) a polyepoxide of molecularweight l0O02000 and (B) a primary or secondary amine containing hydroxylgroups to yield a curable resinous rr 1 ate ri z 1 l There has beengreat interest in developing resinous products which could be cured atlow ambient temperatures in reasonable lengths of time. Much attentionhas been paid to basing these resinous products upon epoxy or modifiedepoxy systems. This is because the polymerized4,4-isopropylidenediphenolepichlorohydrin backbone of the epoxy resinsystem lends excellent properties to a finished coating. Such propertiesinclude good adhesion, excellent resistance to chemicals includingwater, good flexibility and impact resistance as well as good abrasionresistance. Lowtemperature curable coatings prepared from modified orunmodified epoxy systems are of particular importance in the marinefield and in the building trades in temperate climates during the coldmonths. To date, very little progress has been made in this area and infact no commercial epoxy based systems are said to perform a SaQFQrllrfQ .swampsratyreaaizlisati a Several studies have been conductedwhich elaborate on the accelerating effects of alcohols, phenols andprimary amines, tertiary amines and sulfur containing compounds on therate of oxirane group-amine reaction. However, those skilled in the artgenerally agree that none of these resins meet the design critique; ie:low temperature curable epoxy based resinous compositions. Greenlee etal, (1. Thioalkanoic Acids as Epoxy Curing Agents," S. O. Greenlee, G.J. Crocker' and C. L. Weidner, 1. Paint Technol. 42, 31 (1970)) havepresented evidence to show that thioalkanoic acids are satisfactory roomtemperature curing agents for straight epoxy resins. Among the drawbacksto this approach is the odor of the sulfur compounds'utilized andrelatively poor film properties when cured at lower solventF-(Z. R. R.Dileone, J. Polym. Chem. 8, 609 (l970)) (3. J. E. Herweh and W. Y.Whitmore, J. Polym. Chem. 8, 2759 (1970)) Thus, with a polyisocyanatesecondary hydroxyl group in the backbone are used up leaving the epoxygroups largely untouched.

It is, therefore, an object of this invention to provide novel curableresinous compositions of matter which may be cured at low ambienttemperatures.

Another object of this invention is to prepare novel. curable, resinouscompositions of matter based upon a modified epoxy resin which may becured at low ambient temperatures by polyisocyanates while retainingexcellent film properties.

Further objects and the entire scope of applicability of the presentinvention will become apparent from the detailed specification andexamples given hereinafter; it should be understood, however, that thedetailed and specific examples while indicating preferred embodiments ofthe invention are given by way of illustration only, since variouschanges and modifications within temperatures. Similar problems existwith the use of catalyzed polymercaptans as low temperature curingagents. Though mercaptan curing agents are highly reactive with epoxyresins even at very low temperatures the final coating suffers fromodor, poor adhesion and The use of polyisocyanates to cure straightepoxy resins is known to the art; the curing taking place by reactionbetween the isocyanate groups and the secondary hydroxyl groups present.in the high molecular weight epoxy resin. One of the major drawbacks tothis approach is that the consumption of the hydroxyl groups during thecuring process leads to poor adhesion with resultant film failure aswell as brittleness. High molecular weight epoxy resins are required toprovide the. necessary hydroxyl functionality w ich means, that thesolids content of the coating system has necessarily to be kept low.resulting in additional poor adhesion problems, and the like. It hasbeen demonstrated that an isocylanate group does not react with an epoxygroup the spirit and scope of the invention will become apparem to thoseskilled in the art. v p 7 It has now been found that these and otherobjects may be achieved by preparing curable resinous compositionscomprising (A) an organic polyepoxide and (B) an amine selected from agroup consisting of primary and secondary amines containing hydroxylgroups. They may be cured by isocyanates at low temperatures. Thereaction of the OH containing amine component (B) with the epoxycomponent (A) converts the terminal epoxy groups (which are non-reactiveto isocyanates at low temperatures) to hydroxyl bearing groups whichreact relatively fast with isocyanates at low (about? C) temperaturesThese novel compositions may be formulated into coatings which cure atlow ambient temperatures through the use of a polyisocyanate as a curingagent.

It is important to note that this rapid reaction of isocyanate-OH takesplace not only when the substrate is cold but also when the coatingcomposition itself is cold. That is, it is not necessary to maintain thecoating composition at an elevated temperature during the coatingoperation.

The curable resinous compositions of instant invention may be preparedgenerally by charging an'organic polyepoxide and a primary or secondaryamine containing hydroxyl groups into a suitably equipped resin flask.The temperature is rapidly raised to about C under an inert gasatmosphere and with agitation.

These reaction conditions are maintained for a period of time rangingfrom about 2 to 3 hours. At the end of this timethe product is removedand allowed to cool.

A protective coating may be prepared directly from this product bydissolving in a suitable solvent and adding an isocyanate and allowingto cure. Finished films have good adhesion, excellent resistance towater and chemicals, possess good abrasion resistance as well asexcellent flexibility and impact resistance. Typical coatingformulations and their properties are illustrated in Example XXII. I p Hp Organic polyepoxide compounds suitable for the practice of thisinvention comprise those resinous epoxies obtain by the reaction of4,4'-isopropylidenediphenol with epichlorophydrin. The preparation ofthese epoxy resins is widely known and practiced in the art. Themolecular weight for the polyepoxy, component A, may range from about340 to about 4000 or higher; the limiting factor being that thepolyepoxide should be fluid enough at the reaction temperature to insurecomplete mixing and reaction. Preferably the molecular weight shouldrange from about 1000-2000 because subsequent coatings show superiorperformance properties.

Component B may be selected from a wide range of primary and secondaryamines preferably those bearing hydroxyl groups. These include diethanolamine, diisopropanol amine, n-methyl-ethanol amine, naminoethylethanolamine, mono-isopropanol amine, diethylenetriamine, triethylenetetramine, tetraethylene pentamine, propylene diamine, 1,3 diaminopropane, aminobispropyl amine, n-hydroxyethyldiethylene triamine,n-aminoethyl piperazine and the like and mixtures thereof. The preferredamines are diethanol amine or diisopropanolamine, n-aminoethylethanolamine and n-aminoethyl piperazine because of the outstandingresults obtained therewith.

Reaction conditions may vary greatly as to time and temperature. Thelowest reaction temperature is determined by the melting point of theepoxy resin and its fluidity at that temperature. For instance, an epoxyhaving a molecular weight of about 360 is a viscous liquid at roomtemperature and a reaction temperature of about 50 C is thereforepossible. However, the reaction would proceed very slowly and forpractical purposes a lower temperature range of about 100 C ispreferred. At a temperature above 195 C the compositions of thisinvention begin to degrade and therefore this is considered to be thepractical upper temperature range. The reaction time is influenced bythe temperature such that at higher reaction temperatures a shorterperiod of reaction is required. Therefore, within the preferred reactiontemperatures the time of reaction may range from about 3 hours at thelower temperatures to about 1 hour at higher temperatures. At a reactiontemperature of about 175 C 2.5 hours is needed to yield the desiredproduct; this being the preferred time and temperature of the reaction.

Preferably, this reaction is run under an inert gas atomsphere such asnitrogen or carbon dioxide but this is not essential.

These novel, curable, resinous compositions of matter as heretoforedescribed are readily curable at temperatures as low as about C throughthe use of an isocyanate as a curing agent. If an isocyanate having upto two NCO groups is used as the curing agent, a film is produced havingmediocre properties. Whereas a polyisocyanate curing agent produces ahard, tough film having excellent physical properties. Since many of theproducts of this invention are solids at room temperature they must befirst dissolved in a suitable solvent before the curing agent is added.

lsocyanate curing agents which function as low temperature curing agentsfor the curable resinous compositions of matter of this invention may beselected from a group including toluene diisocyanate-neopentyl glycoladduct, toluene diisocyanate-pentaerythritol adnate-neopentyl adduct,polymethylene polyphenylisocyanate-pentaerythritol adduct, polymethylenepolyphenylisocyanate-glycerol adduct, toluene diisocyanate, isophoronediisocyanate and polymethylene polyphenylisocyanate and the like.

However, excellent results have been obtained through use of thereaction product of toluene diisocyanate and trimethylol propane as thecuring agent and this is preferred. The amount of curing agent employedmay be based upon the number of mols of resin used. Depending upon theNCO content of the curing agent, the mol ratio of resin to curing agentmay range from about 1:1 to about 1:4. The preferred mol ratio of resinto curing agent is about 122.5.

Solvent may be added to the curing agent to facilitate mixing of theresin but is not essential. Excellent coating formulations based uponthe novel curable resinous compositions of instant invention may beprepared utilizing the various fillers, pigments, solvents and otheradditives known to those skilled in the art.

For example, it has been found that fillers such as talcum, clays,carbonates, asbestos powder, quartz powder, chalk, dolomite, kieselguhr,heavy spar and mixtures thereof may be used.

For coloring the mixtures according to the present invention, it ispossible to use dyes and/or inorganic pigments. An illustrative digestof pigments suitable for this purpose are set forth for example inOrganic Protective Coatings, Reinhold Publishing Corp. 1953, pages -166inclusive.

In addition, flow control agents, accelerators such as triethylamine anddibutyltin dilaurate and the like may be compounded into the coatingformula.

A large variety of solvents may be used for the resin and for coatingsincluding diacetone alcohol, methylisobutyl ketone, methylethylketone,dioxane and methylene chloride and mixtures thereof. It has been foundthat a mixture of dioxane and methyl isbutyl ketone, 50/50 by weightperforms satisfactorily.

The invention will be more readily understood by reference to theaccompanying specific examples which are intended as illustrative onlyrather than as limiting the invention except as defined in theaccompanying claims.

Preparation of Curable Resinous Compositions EXAMPLE 1 Into a two literresin flask fitted with a means for stirring, thermometer, inert gasinlet, reflux condenser and heating mantle was charged 1,000 grams of a4,4- isopropyl-idenediphenol-epichlorohydrin epoxy resin having anaverage molecular weight ranging from about 1,750 to 2,000 and 120 gramsof diethanolamine. The temperature was raised to C with stirring under anitrogen atmosphere. These reaction conditions were maintained for 2.5hours at the end of which the resinous product was poured into a shallowtray and allowed to cool into a hard mass.

EXAMPLE II [n the following Examples both the reactants and the reactionconditions were varied while using a reaction setup as described inExample 1. The epoxy resin used in each instance was a4,4-isopropylideneepichlorohydrin type of different average molecularweight.

TABLE I Epoxy M ol Wt. No. Grams No. Grams Reaction Reaction Example(Approximate) Epoxy Amine Amine Temp. C Time/Hrs. No.

360-390 390 diisoptopanol amine 280 190 1.5 11 360-390 390 isopropanolamine 165 100 3.0 111 900-1050 1000 diethanol amine 230 175 2.5 I\'900-1050 1000 n-hydroxyethyl diethylene triamine 325 175 2.0 V 1125-1450 1500 diethylene triamine 227 175 2.5 \'I 1750-2000 2000diisopropanol amine 280 175 2.5 \11 1750-2000 2000 n-hydroxyethyldiethylene triamine 325 175 2.5 \'III 1750-2000 2000 n-aminoethylethanolamine 228 175 2.5 IX 1750-2000 2000 diethylene triamine 227 1752.5 X 1750-2000 2000 propylene diamine 165 175 2.5 X1 1750-2000 2000n-amino ethylethanol amine 230 175 15 X11 1750-2000 2000n-amino-ethyl-piperazine 286 175 2.5 Xlll 1750-2000 2000 tetraethylenepentamine 418 175 2.5 XIV 1750-2000 2000 triethylene tetramine 321 1752.5 XV 1750-2000 2000 isopropanol amine 165 175 2.5 XVI 1750-2000 2000diethanol amine 230 175 1.0 XV11 3100-4000 340 diethanol amine 115 1903.0 XVIII 340 340 diethanol amine 230 150 2.5 X1X C under a nitrogenblanket with stirring. These reaction conditions were maintained for 6hours at which time the light yellow viscous solution was poured into acontainer and sealed under nitrogen.

Preparation of Coatings from Resins Prepared According to Examples 1 XIXEXAMPLE XXI A low temperature curing coating was prepared as follows:

Resin from Example 1 1060 grams Dioxane 800 grams MIBK 800 grams 0 Theresin was broken into lumps and added to the dioxane with stirring andheat to hasten solution. To this solution was added the 800 grams ofMIBK with stirring to obtain a percent N.V. solution.

The trimethylol propane-to]uenediisocyanate adduct' prepared accordingto Example XX was diluted to 40 percent N.V. using dioxane.

266 grams of the resin solution and 56 grams of the curing agentsolution were separately cooled down to 5 C by packing the containers inice, and leaving them in the cold room (temperature 6-8 C) over-..

night, and again packing the containers in ice for two Just prior tospraying, the two ingredients were mixed and stirred to a homogeneoussolution. This solution was sprayed onto Parker EP-l (4. These panelsare available from Hooker Chemical Co., Parker Division, Detroit,Michigan.) panels.

Parker EP-l panels are steel panels with a microcystalline zincphosphate surface, which would, for screening purposes, approximate thetype of substrate encountered for marine coatings use.

Panels were set up in the spray booth, and the mixture sprayed evenly onthe panels, and the panels immediately transferred to the cold room andallowed to cure at 6-8 C. (The panels were not precooled in the coldroom before spraying, in order to avoid formation of a moisture film onthe panels when exposed to room temperature humidity).

The curing of the panels was followed every few minutes. They were dryto touch in approximately 25 minutes. Panels were cured overnight at 68C and the development of solvent resistance was followed by testing aspot on the panels with drops of MIBK, allowing to stand for a fewseconds, and then attempting to scratch the film. The panels withstoodthis test after approximately 24 hours in the cold room.

Preliminary tests for adhesion by making a cut in the film with a sharpinstrument and attempting to remove it from adhesive tape made no changein the film, indicating satisfactory adhesion. Also when the panels weresubjected to the bend test, no signs of film cracking or weakness wereobserved.

EXAMPLE XXII amount of curing agent were changed. The levels of resin tocuring agent were based upon resin solids.

mols Resin According mols curing I Physical To Example No. resin CuringAgent Agent Properties* IX 1 TDl-neopentyglycol l A XVII 1TDl-neopentyglycol l A VII 1 TDl-TMP 1.2 A 1V 1 TDl-TMP 4 A ll 1 TD] 3 BX111 1 TDl-TMP 2.2 A XVI l TDl-TMP 2.2 A I 1 TDI-pentaerythrital 1.8 A Il TDI-glycerol 2.3 A

A- acceptable s A B- unacceptable TDltoluene diisocyanate TMP-trimethylol propane EXAMPLE XXlll In order to completely evaluate theresins of this invention for use in marine and similar low temperaturecoating applications the following two component grey hull enamel wasformulated and evaluated as follows:

The results of the evaluation'are presented in the following tables.

TABLE ll ADMIXED GRAY HULL ENAMEL Formulation Lbs/350 gallons OH/NCORatio 2:] COMPONENT -A; Total Solids (percent by weight of enamel) 49.9Epoxy according to Example I 600.0 Non-Volatile Vehicle (percent byweight of vehicle) 32.] (Solids) Viscosity No. 4 Ford Cup (seconds at5C) 70.0 Di 4500 Viscosit (Stormer) (Krebs Units at 5C) 68.0 MIBK 4500Dry Film Thickness (.004 inch wet film on T l 345 Bonderite I00) (mils)[.15 Calcium carbonate 285.0 Cure time at 5C Titanian dioxide l72.5Carbon Black l L25 Set-to-touch (minutes) l5.0 Grind 16 hours in steelball mill to fineness 6+N.S. and free (hwrs) P P Reduced Viscosity No. 4Ford Cup (seconds) add:

Dioxane 225.0 4 parts Enamel. 1 part Dioxane by volume 24.0 MIBK 225.0

Spraying Properties at reduced viscosity using Pounds per gallon [0.2581763.75 269.4 (Siphon yp y mixed cHamel) y good gals. 20 RecoatabilityAt Z-Vz hrs curing at 5C very good Procedure: epoxy solids, two-thirdsof solvent and all Pm Life at 22 Curmg S C g i fr z the pigment wereadded to a steel ball mill, ground for 16 hrs. or to a fineness of6+N.S. Balance of solvent was added and mixed for 15 minutes.

Application Procedure COMPONENT -B: 25 Parker bonderite I00 panelscoated with (draw down 4 mils wet film) the hull C i agent according toenamel containing primary OH/NCO ratio of 2:]. Example XX at 7, N\/' 7 1The gray hull enamel and curing adduct were separately cooled down to0-$C in Dioxanc 154.0 a regrtgerator OVCl'nlghL Just prior to conductingexperiments. the two components were Pounds p g 9.269 330.0 35'6 glglleglflnd packed "110C to matntatn a temperature of application.

Admixed Enamel OH/NCO 2:]

Pounds Gallons COMPONENT A (Epoxy) 2,764.0 269.4

COMPONENT B (Curing 330.0 35.6 Adduct) Pounds per Gallon 10144 3.0940305.0

Application by drawdown blade and spray-gun were made 0 er precooledpanels and stored in regrigerator maintained at a temperature of 5C forcuring times of 3. 7 and 14 days.

Baked films were stored overnight at a temperature of 5C then baked forone hour at 320F.

These panels are available from Hooker Chemical Co. Parker Division.Michigan. Parker Bonderite I00 panels are ztnc phosphated cold rolledsteel plates 4 inches X l2 inches.

TABLE Ill Application with draw-down blade at 4 mils film (wet) CuringTime: days 7 days 14 days Baked Curing Temperature 5C 5C 5C 1 hr at 320FDry film thickness (mils) 1.3 1.3 1.2 1.15

Pencil hardness 3B-0 3B-2B-l 3B2B-l 6H- l0 Adhesion (cross hatch) (tape)excellent excellent excellent excellent Flexibility (conical madrel)excellent excellent excellent cracking /4" from end ResistanceProperties:

Dioxanc softens. softens. softens. softens, (5 minutes) recoversrecovers recovers recovers 2 hrs. 2 hrs. 2 hrs. 2 hrs. MlBK (5 min.) noeffect no effect no effect no effect 20% NaOH no effect no effect noeffect no effect (60 min.) NaOH no effect no effect no effect no effectmin.) Impact: l l0 l l0 120 40 50 Direct (in.-lbs.) Impact: 90 80 90 4 8Reverse TABLE n w Curing Time: days days 14 days Baked Abrasion 105 l I90 95 80 85 60 65 (Falling sand) (liters) Water Resistance (7 daysimmersion) Film Tested I hour after removal Cure Time: 3 days 7 days l4days Baked Above Water Line: Knife Test Ribbons Ribbons Ribbons RibbonsPencil Hardness F-H-S F-H-S F-H-S 6H- l() Adhesion (cross hatch) (tape)excellent excellent excellent excellent Blushing sl. -cons. sl. -cons.sl. cons. none Chalking none none none none Blistering none none nonenone Below Water Line: Knife Test Ribbons Ribbons Ribbons Ribbons PencilHardness B-HB-3 B-HB-3 B-HB-3 6H- I0 Adhesion (cross hatch) v (tape)excellent excellent excellent excellent Blushing severe severe v severenone Chalking none none none none Blistering none none none noneWeatherometer Resistance (films checked immediately after removal) CureTime: 3 days 7 days 14 days Baked Film Gloss Film Gloss Film Gloss FilmGloss Initial Gloss 26 25 25 Exposure I00 hr. Good 23 Good Good l6 Good5 200 hr. Bluah- Blush- Blush- Blushing 16 ing I0 ing 14 in; 2 300 hr. 32 3 l 400 hr. l l i TABLE IV LOW TEMPERATURE GRAY HULL ENAMELApplication by Spraying, one wet coat Cure Time: 3 days 7 days 14 daysBaked Curing temperature 5C 5C 5C l hr at 320F Dry film thickness (mils)L5 1.5 L6 1.5 Pencil hardness 3B-O 3B-O 3B-2B-l 6H- l0 Adhesion (crosshatch) (tape) excellent excellent excellent excellent Flexibility(conical mandrel) excellent excellent excellent l-Vz inch crackingResistance Properties: 3 days 7 days 14 days Baked Dioxane softens,softens, softens, softens. (5 min.) recovers recovers recovers recovers2 hrs. 2 hrs. 2 hrs. 2 hrs. MlBK no effect no effect no effect no effect(5 min.) 20% NaOH no effect no effect no effect no effect (60 min.) NaOHno effect no effect no effect no effect min.) 1 Impact: Di t (i -thl()()- l l(l 3()- 4(l Impact: Reverse (in.-lbs.) 80 60- 70 3()- 40 4Abrasion (Falling Sand) (Liters) ]25. l30 l30- l35 75- 80 TABLE IV LOWTEMPERATURE GRAY HULL ENAMEL Application by Spraying, one wet coat CureTime: 3 days 7 days l4 days Baked Water Resistance (7 days immersion)Film Tested One Hour After Removal Cure Time: 3 days 7 days 14 daysBaked Above Water Line: Knife Tent Ribbons Ribbons Ribbons RibbonsPencil Hardness B-HB-3 B-HB-3 B-HB-3 6H- l Adhesion (cross hatch) (tape)excellent excellent excellent excellent Blushing sL-cons. sl.-cons.sl.-cons. none Chalking none none none none Blistering considerableconsiderable considerable none Below water Line: Knife Tcst RibbonsRibbons Ribbons Ribbons Pencil Hardness 3B-O 3B-0 3B-0 6H- l 0 Adhesion(cross hatch) (tape) excellent excellent excellent excellent Blushingsevere severe severe v. slight Chalking none none none none Blisteringnone none none none Wcatherometer Resistance (films checked immediatelyafter removal) Cure Time: 3 days 7 days l4 days Baked Film Gloss FilmGloss Film Gloss Film Gloss Initial Gloss 26 25 5 Exposure 100 hr. Good22 Good 14 Good l3 Good 5 200 hr. Blushing l0 Blushing l0 Blushing l3Blushing 2 What is claimed is:

1. An epoxy composition produced by reacting (l) the reaction product of(A)4,4isopropylidene diphenolepichlorohydrin epoxy resin having amolecular weight ranging from about 1,000 to about 2,000 and (B) anamine selected from the group consisting of diethanol amine,diisopropanol amine, n-aminoethyl piperazine and n-aminoethyl ethanolamine and (ll) a curing agent for (l) consisting of the toluenediisocyanate adduct of a polyol selected from the group consisting oftrimethylol propane, pentaerythritol and glycerol in the p n r fl ll) awvs tf (11294.!!!) hi

2. The composition according to claim 1 wherein the mol ratio of (I) to(II) is about 1:2.5.
 3. The compositions according to claim 1 whereinfillers and pigments are added.
 4. The compositions according to claim 1wherein the amount of fillers and pigments added range up to about 200parts by weight for each 100 parts by weight by (I) and (II) used.